The present invention relates to novel reactive dyes, to processes for the preparation thereof and to the use thereof in dyeing or printing textile fibre materials.
The practice of dyeing using reactive dyes has recently led to higher demands being made in terms of the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.
Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.
The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes that possess the qualities characterised above to a high degree. The novel dyes should especially be distinguished by high fixing yields and high fibre-dye bond stability; it should also be possible for dye that is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good all-round fastness properties, for example light-fastness and wet-fastness properties.
It has been shown that the problem posed is largely solved by the novel dyes defined below.
The present invention accordingly relates to reactive dyes of formula (1) 
wherein
R1 and R2 are each independently of the other hydrogen or unsubstituted or substituted C1-C4alkyl,
R3 and R4 are each independently of the other hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, carboxy or sulfo,
R5 and R6 are each independently of the other hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, nitro, C2-C4alkanoylamino, benzoylamino, ureido, carboxy or sulfo,
D is a radical of formula 
wherein
(R7)0-2 denotes from 0 to 2 identical or different substituents selected from the group halogen, C2-C4alkanoylamino, C1-C4alkyl and C1-C4alkoxy,
X is halogen,
Axe2x80x94Y is a radical of formula 
wherein
Y1 is xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino and
Z1 and Z2 are each independently of the other vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl,
m is the number 1, 2 or 3, and
n is the number 1 or 2, with the proviso that
D is a radical of formula (3) when Axe2x80x94Y is a radical of formula (4b).
As C1-C4alkyl for R1, R2, R3, R4, R5, R6 and R7, each independently of the others, there come into consideration, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl or ethyl, and especially methyl. The alkyl radicals R1 and R2 mentioned may be unsubstituted or substituted, for example, by hydroxy, sulfo, sulfato, cyano or by carboxyl. Preference is given to the corresponding unsubstituted alkyl radicals.
As C1-C4alkoxy for R3, R4, R5, R6 and R7, each independently of the others, there come into consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and isobutoxy, preferably methoxy or ethoxy, and especially methoxy.
As halogen for R3, R4, R5, R6 and R7, each independently of the others, there come into consideration, for example, fluorine, chlorine and bromine, preferably chlorine or bromine, and especially chlorine.
As C2-C4alkanoylamino for R5, R6 and R7, each independently of the others, there come into consideration, for example, acetylamino and propionylamino, especially acetylamino.
As a radical of formula (2), D in the reactive dyes of formula (1) according to the invention is, for example, a radical of formula 
preferably of formula (2.14), (2.15) or (2.16), and especially of formula (2.14).
As a radical of formula (3), D in the reactive dyes of formula (1) according to the invention is, for example, a radical of formula 
preferably of formula (3.11) or (3.12), and especially of formula (3.12).
For X there come into consideration, for example, fluorine, chlorine and bromine. R1 and R2 are preferably, each independently of the other, hydrogen or C1-C4alkyl, especially hydrogen or methyl, and more especially hydrogen.
R3 and R4 are preferably, each independently of the other, hydrogen, C1-C4alkyl, C1-C4-alkoxy or sulfo, especially hydrogen, C1-C4alkyl or C1-C4alkoxy, and more especially hydrogen.
R5 and R6 are preferably, each independently of the other, hydrogen, C1-C4alkyl, C1-C4-alkoxy, C2-C4alkanoylamino, benzoylamino, ureido or sulfo, especially hydrogen, C1-C4alkyl, C1-C4alkoxy, ureido, C2-C4alkanoylamino, and more especially hydrogen.
R7 in radical D of formula (3) preferably denotes from 0 to 2 identical or different substituents selected from the group C1-C4alkyl and C1-C4alkoxy and is especially hydrogen.
X is preferably fluorine or chlorine, especially fluorine.
m in radical D of formula (2) is preferably the number 2 or 3 and especially the number 3.
n in radical D of formula (3) is preferably the number 2.
Preference is given to the reactive dyes according to the invention wherein
m is the number 2 or 3,
n is the number 2, and
R7 is hydrogen.
Z1 and Z2 are preferably, each independently of the other, vinyl or xcex2-chloroethyl. In the radicals of formula (4b), the fibre-reactive group xe2x80x94COxe2x80x94NHxe2x80x94(CH2)2xe2x80x94SO2xe2x80x94Z2 is preferably in the 3-position. Preferably, the radical of formula (4b) does not contain a sulfo group on the benzene ring.
In an especially preferred embodiment of the reactive dyes of formula (1) according to the invention, the radical of formula xe2x80x94Axe2x80x94Y is a radical of formula (4a) or (4b), especially of formula (4a).
In a preferred embodiment of the present invention, the reactive dye of formula (1) is a reactive dye of formula 
especially of formula (1a).
The present invention relates also to a process for the preparation of the reactive dyes according to the invention, wherein a compound of formula 
cyanuric halide and an amine of formula 
are reacted with one another in any order, the definitions and preferred meanings given above applying for R1, R2, R3, R4, R5, R6, Axe2x80x94Y and D.
Because the process steps mentioned above may be carried out in different orders as well as, where appropriate, simultaneously, different process variants are possible. The reaction is generally carried out stepwise, the order of the simple reactions between the individual reaction components advantageously being determined by the particular conditions. For example, approximately 1 molar equivalent of an amine of formula (6) is reacted with approximately 1 molar equivalent of cyanuric halide and the product obtained is then condensed with approximately 1 molar equivalent of a compound of formula (5). In another process variant, for example, approximately 1 molar equivalent of a compound of formula (5) is reacted with approximately 1 molar equivalent of cyanuric halide and the condensation product obtained is then condensed with approximately 1 molar equivalent of an amine of formula (6). Instead of the dye of formula (5), it is also possible to use its precursor and to complete its preparation in the course of the subsequent process by diazotisation followed by a coupling reaction.
The individual condensation reactions are carded out, for example, according to methods known per se, generally in aqueous solution, at a temperature of, for example, from 0 to 50xc2x0 C., especially from 0 to 10xc2x0 C., and at a pH of, for example, from 3 to 10, especially from 3 to 7.
As cyanuric halide there are suitable, for example, cyanuric chloride and cyanuric fluoride, especially cyanuric fluoride.
The end product may optionally be subjected to a further transformation reaction. Such a transformation reaction is, for example, conversion of a reactive group, present in Y, that is to say in Z1, Z2 or Y1, and capable of conversion into a vinyl group, into its vinyl form by treatment with dilute sodium hydroxide solution, e.g. conversion of the xcex2-sulfatoethylsulfonyl or xcex2-chloroethylsulfonyl group into the vinylsulfonyl radical. Such reactions are known per se. Preferably, vinylation is carried out.
The preparation process for the reactive dyes according to the invention is preferably carried out by reacting approximately 1 molar equivalent of a compound of formula (5), wherein the definitions and preferred meanings given above apply for R1, R3, R4, R5, R6 and D, with approximately 1 molar equivalent of cyanuric chloride or cyanuric fluoride, preferably cyanuric fluoride, and condensing the resulting condensation product with approximately 1 molar equivalent of a compound of formula (6), wherein the definitions and preferred meanings given above apply for R2 and A, and wherein Y contains a reactive group capable of conversion into a vinyl group, and converting the said reactive group into its vinyl form.
The compounds of formulae (5) and (6) are known or can be prepared analogously to known compounds.
The reactive dyes of formula (1) according to the invention are present either in the form of their free acid or, preferably, in the form of their salts. Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts or salts of an organic amine. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts or a mono-, di- or tri-ethanolamine.salt.
The compounds of formula (1) according to the invention are suitable as dyes for dyeing and printing a wide variety of materials, such as hydroxyl-group-containing or nitrogen-containing fibre materials. There may be mentioned, as examples of nitrogen-containing fibre materials, silk, leather, wool, polyamide fibres and polyurethanes. The reactive dyes according to the invention are especially suitable for dyeing and printing all types of cellulosic fibre materials. Such cellulosic fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose, preferably cotton. The reactive dyes according to the invention are also suitable for dyeing or printing cellulosic blend fabrics, for example blends of cotton and polyamide fibres or especially cotton/polyester blend fibres.
The reactive dyes according to the invention can be applied to the fibre material and fixed to the fibre in a number of ways, especially in the form of aqueous dye solutions or dye print pastes. They are suitable for the exhaust process and also for dyeing using the pad-dyeing process, according to which the goods are impregnated with aqueous, optionally salt-containing, dye solutions and the dyes are fixed, after treatment with an alkali or in the presence of an alkali, optionally under the action of heat or as a result of being kept at room temperature for several hours. After fixing, the dyeings or prints are thoroughly rinsed with cold and hot water, optionally with addition of an agent that has a dispersing action and promotes diffusion of unfixed dye.
The reactive dyes according to the invention are distinguished by high reactivity, good fixing characteristics and very good build-up characteristics. They can therefore be used in the exhaust dyeing process at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The dyes according to the invention are also especially suitable for printing, especially on cotton, but also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics containing wool or silk.
The dyeings and prints produced using the reactive dyes according to the invention have a high tinctorial strength and a high fibre-dye bond stability in both acidic and alkaline ranges, and they also have good light-fastness and very good wet-fastness properties, such as fastness to washing, to water, to seawater, to crossdyeing and to perspiration, as well as good fastness to chlorine, to pleating, to hot pressing and to rubbing.